Preferential adsorption of normal paraffins on graphite



United States Patent ()filice 3,338,815 Patented Aug. 29, 1967 3 338 815 PREFERENTIAL AfisoizPTioN OF NORMAL PARAFF INS ON GRAPHITE Aleksauder Jerzy Groszek, Ealing, London, England, as-

the amount of selective adsorption, which increases with the polarity of the solvent.

The chain length of hydrocarbons separable according to the method of the present invention will also depend signor to The British Petroleum Company Limited, 5 to a certain extent on the solvent, the more polar the sol- Lolldoll, j f a cofpol'atloll Of g and vent the shorter will be the shortest chain length of hydro- N a i'f 1 1: 1 gg 4 carbon which can be adsorbed. For example using nalms gg i 2 'g1 i32 gg ga gg' heptane, hydrocarbons of C and above can be adsorbed 9 Claims. (CL 10 ghlerggsagssnfieeithyl alcohol hydrocarbons as low as C This application is a continuation-in-part of copend- The efiiciency of adsorption has, moreover, been found ing application Ser. No. 490,092, filed Sept. 24, 1965, now to increase with increasing chain length. abandoned. Subsequent desorption of the selectively adsorbed hy- This invention relates to the separation of long-chainv drocarbons may be effected by any of the customary normal hydrocarbons from their mixtures with other hymethods, for example, by flushing with an excess of a drocarbons, particularly from petroleum fractions. solvent such as benzene, heating, or evacuating.

According to the present invention a method of separat- The process of the present invention may be utilized, ing long-chain normal hydrocarbons having at least 10 for example, for the isolation and concentration of comcarbon atoms per molecule from their mixtures with other pounds with long normal parafiinic chains from heavy hydrocarbons comprises contacting the mixture with petroleum distillates. In particular, however, the process graphite having a surface area of at least 50 m. /gm., to is useful for the reduction of cloud points and pour points adsorb selectively the normal hydrocarbons. of petroleum fractions and for dewaxing petroleum frac- Preferably the separation is carried out in the presence tions especially to produce fractions having high viscosity of a solvent which is lower-boiling than the feedstock, indices and also low sulphur contents. particularly one of the common solvents for highboiling The invention is illustrated with reference to the folhydrocarbons, for example benzene, n-heptane, iso-octane, lowing examples: ethyl alcohol, or petroleum ether. Example 1 The mixture 18 preferably contacted with the graphite 103 grams of a 160/95 grade lubricating Oil derived in the form of a dilute solution, preferably containing v from mixed Kuwait and Iraq crude oils were dissolved between 0.01% and 10% (weight per volume) of the in 100 mls. of iso-octane and the solut on slurried with normal hydrocarbons. Within this range the amount of h d Ibo d Orbed increases with the concentra 19.5 grams of a synthetic graphite ground in air to a BET 353 j S surface area of 450 m. g. The slurry was filtered at am- The amount of hydrocarbon adsorbed increases with blept temperauir? a produq contammg 75% by Weight of the original oil was obtained. The filter was then the surface area of the graphite, and the surface area is o washed with toluene at 80 C. when a further product preferably, therefore, as high as possible preferably f 2517 ht f th a1 bt d Th within the range 50900 m. /gm., particularly 300-700 Ormmg Welg o fi 9 f e mF/gm. The surface area of the graphite may be inresults are summanzed mt e o owmg Tab 6 creased, for example, by grinding it. Oleophilic graphite 40 Examplg 2 as defined below is preferred.

The amount of preferential adsorption also varies ingr ams of 2 5 g? 2: defied from zarzstlge versely with temperature, and preferably the adsorption O11 (1185? m 0 an t e is carried out at a temperature within the range C. Solutlon Slumed 11th grams of the gTaPhlte of to 0 ample 1. The procedure of Example 1 was then repeated.

The nature of the solvent has also been found to affect 45 The results are summarized in Table 2 below:

TABLE 1 Viscosity, cSt Carbon Type Analysis Product, percent wt. of feed vislfgggy Pong Eomt, pgipllguvrt Colour 100 F. 210 F. 1 N A (by filtration) 96.49 10. 44 98 15 0.62 64 33 3 Water White.

' 104 5 Yellow. i881 96 0 1. 14 66 30 4 Do.

TABLE 2 Viscosity, cSt Carbon Type Analysis Product, percent wt. of feed Visfgtsagy Poug goint, pgil glurt' Colour F. 210 F. Cp C CA 65 (by filtration) 38.40 5.66 as 15 Water White.

" 32. 67 5. 39 +10 Yellow. 36. 66 5.60 99 +4 D0.

Example 3 5.05 grams of a naphthenic/paraffinic fraction obtained by selective solvent extraction of the 160/95 grade oil of Example 1 were dissolved in 50 mls. of iso-octane and the solution slurried with 21 grams of the graphite of Example 1. The procedure of Example 1 was then repeated. The results are summarized in Table 3 below:

The above data indicate that Agha Jari waxy distillates yield 5 to by weight of oil with a sulphur content of 0.1-0.2% weight and a pour point below 60 C.; the yield of oil with a pour point of +10 F. is higher, between and with the sulphur content varying between 0.1 and 0.4% weight. All these oils are either water White or very pale yellow.

TABLE 3 Viscosity, 081; Carbon Type Analysis Product, percent wt. of feed Viscosity Pour Point, Sulphur, Colour Index F. percent wt. 100 F. 210 F. Cp C C 65 (by filtration) 89. 29 10. 01 100 63 37 0 Water White. 33 (by elution with hot toluene 66. 51 9. 22 120 75 25 0 Straw Yellow. Feed 74. 5 9. 37 110 67 33 0 Water White.

Example 4 The volume of solvent required to elute the desired oil 4 grams of a waxy railinate obtained by the selective solvent extraction of the lubricating oil feedstock of Example 1 were dissolved in mls. of petroleum ether and the solution slurried with 17 grams of the graphite of Example 1. The procedure of Example 1 was then repeated. The results are summarized in Table 4 below:

fractions at room temperature was 150 ml. out of a total of 75 0 ml. necessary to displace all the oil from 90 grams 30 of graphite.

TABLE 4 Viscosity, cSt Carbon Type Analysis Product, percent wt. of feed Viscosity Pour Point, Sulphur, Colour Index F. percent wt. 100 F. 210 F. Cp O C 47 (by filtration) 91.95 10. 06 +5 0.48 64 33 3 Water White. Feed Solid at room temperature 100 1. 05 Dark Yellow.

Example 5 An Agha Jari waxy distillate was treated with graphite having a BET surface area of 500 m g. in a chromatographic column with a succession of solvents which are indicated, with the results obtained, in the following 50 For a final =hot elution stage for example benzene, as in Table 5: the 90 grams of graphite.

TABLE 5 Feedstock, 21.0 g. Pressure Drop, 50 p.s.i. Graphite, 90.0 g. Column Height, 10 in. Eluent Flowrate, 50 ml./h. Column Diameter, 1% 1n. Cumulative, Cloud Pour Viscosity, cSt I percent oil Solvent Volume, ml. Point, Point, Sulphur, Viscosity Colour Eluted F. F. percent Index 9 Petroleum ether, 50 1 45 0.1 Water White. 17 Petroleum ether, 2 8 10 0.3 Do. 29. Petroleum ether, 50. 27 30 0. 6 Straw Yellow. 40".. n-C 100 47 50 0.9 Do. 56 1-. n-C 500 57 60 1. 0 D0. 68 Benzene, 500 66 2. 5 Dark Yellow. 95 Hot C.) benzene, ca. 3 Yellow.

Example 6 A Libyan waxy distillate was treated in a manner similar to that employed in Example 5 as indicated in Table 6 below:

6 Example 8 High yields of low cloud and pour point oil can be obtained by using a mixture of benzene and alcohol as solvent throughout the separation. When Middle East TABLE 6 Feedstock, 20.15 g. Pressure Drop, 50 p,s.i. Graphite, 85 g. Column Height, in. Eluent flow rate, 50 mL/hr. Column Diameter, 1% 1n.

7 Viscosity cSt Cumulative, Solvent Volume, ml. Pour Point, Viscosity Colour Percent Oil Eluted F. Index Aviation Alkyate (Av. Alk.), 42 -70 Water White.

v. Alk., 50 25 18.77 3 79 100 D0. Av. Alk., 50 +25 13.11 3 117 Do. Av. A1k., 50 Do. Av. Alk., 50 Do. Hot (80 C.) Av. Alk., 100- a Do. Hot (80 0.) Av. Alk., 70. Do. Hot (80 C.) Benzene, 200 Yellow. 99.8 Hot (80 C.) Benzene/Ethanol, 200 o. Feedstock. I 100 4. 26 90 Do.

. 1 Solid at room temperature.

Example 7 following results, shown in Table 7,

Waxy distillates are used, this process gives high yields of oils with very low cloud points but relatively high S and aromatic contents. Details of fractionation in a chromatographic column by this method of an Agha Jari waxy distillate are given in Table 8.

Example 9 When graphite is used for the treatment of mineral oils free from aromatic and sulphur compounds, it preferentially absorbs components with a high percentage of carbon atoms in long methylene chains, i.e. the compounds With a relatively high pour point and high viscosity index. An illustration of such treatment is given in Table 9.

Graphite, 90 g. (used previously 6 times). Solvent, Iso-octane.

TABLE 7 Viscosity, cSt Cumulative, Percent Oil Product Solvent Volume, ml. Pour Viscosity Sulphur, Point, Index Percent F. 100 F. 210 F.

' 30 (filtered) 60 (petroleum ether) 0 71. 3 8. 46 97 1. 24 95 (eluted 150 (hot (80 C) toluene) 1 +70 I Feedstock 1 +70 93 03 9.21 77 2 71 Above.

TABLE 8 I Feedstock, 25 g. Pressure Drop, p.s.i. Graphite, 90 g. 4 Column Height, 10 in. Solvent, 20% ethanol in benzene. Column Diameter, 1% in.

Cumulative Solvent Viscosity, cSt Percent Oil Volume, Cloud Point, Pour Point Viscosity Sulphur, Colour Eluted ml. F. F. Index Percent 5O -35 7 Yellow. 50 l8 -15 99.71 9 54 75. 5 1.2 D0. 50 26 30 111 9 99 1. 64 Dark Yellow. 600 at C. ca 120 ca. 3 Do.

TABLE 9 Feedstock, 25.8 g. Pressure, 50 psi.

Column Height, 10 in. Column Diameter, 1 ,43. in.

Viscosity, cSt Cumulative, Percent Solvent Volume, Cloud Point, F. Pour Point, F. Viscosity Index on Eluted ml.

95.0 1 400 ca. +25 45. 61 7.08 122 Feedstock ca. +10 57. 15 7. 65 106 '1 Hot (80 C.) iso-octane.

Example The treatment of mineral oils, substantially free from aromatic and sulphur compounds, can be carired out also by mixing 50 parts of the oil with 100 parts of graphite in a light paraffinic solvent. About 70percent of the oil remains in the filtrate and constitutes the low cloud point portion; the adsorbed material, which can be desorbed with the same solvent at about 100 C., and has an increased viscosity index compared with the original oil. Naphthene and paraffin portion from a Kuwait BG 160/95 10 perature of the The grinding may be carried out in any suitable grinding mill or device and it is desirable to continue the grinding until an oleophilic graphite having a surface area (as determined by nitrogen adsorption) of from to 800 square metres per gram is obtained. For use inthe separation method of the present invention, the surface area should be at least 50 m. /=gm. and preferably at least about 300 m. gm. Usually this can be achieved by grinding at normal temperatures for the required period but the temmixture may be artificially increased if treated in this way gave the following fractions. desired, for example, up to 250 C.

TABLE 10 Viscosity, eSt Cumulative Percent Oil Product Solvent Pour Point, Viscosity Volume, ml. C. Index 70 (filtered) 250 20 71. 24 9. 07 110 30 (eluted)-. 400 (90 C.) 62. 76 8. 86 121 Feedstock +5 79. 56 9. 72 109 Example 11 Similar results are obtained by treating commercial technical white oils. Oils with cloud points below 60 F. can be obtained similarly by decreasing the ratio of oil to graphite to 1:5. The yield of such an oil is about 30 percent weight of the feedstock. Thus naphthenes and paraffins from a BG 150/75 oil treated with graphite yields 32 percent of oil with a cloud point below 60 F. and VI of 98.

A particularly desirable form of graphite for use in this invention is prepared by grinding natural or synthetic graphite in an organic liquid. This graphite product can conveniently be referred to as oleophilic graphite to distinguish it from conventional forms of graphite.

In preparing oleophilic graphite, the starting material may be natural or synthetic graphite. Both these materials are well-known and readily available. The synthetic material is produced from petroleum coke usually by heating to around 2500 C. in a vacuum or inert gas. Typically it contains from 95 to 100% wt. carbon. The natural material may have a slightly lower carbon content than this and usually has a larger crystal size.

Satisfactory oleophilic graphite can be obtained by grinding in most organic liquids but it is desirable to use one the bulk of which can be easily removed from the oleophilic graphite. Those liquids distilling below 500 C. and having .a viscosity below 600 centistokes at 100 F. are therefore preferred. Suitable organic liquids are the hydrocarbons such as n-heptane, iso-octane, toluene, hexadecane and hydrocarbon fractions obtained by the distillation of petroleum, for example, lubricating oil. Other organic liquids that may be used include most volatile oxygen-, halogen-, nitrogenand sulphur-containing organic liquids, for example isopropyl alcohol and carbon tetrachloride. Liquids that react with graphite under the conditions of the treatment should of course not be used. For best results, the amount of graphite in the graphite/ organic liquid mixture should not exceed 50% wt.; preferably it should be from 2 to 20% wt.

One of the quickest and most effective techniques is to carry out the grinding in a vibratory ball mill.

It is desirable to exclude air so far as possible during the grinding operation and this can be most easily achieved by filling the mill with the organic liquid first, followed by the balls and graphite. A suitable procedure is to fill the mill with the liquid, add half the balls, then the graphite and finally the rest of the balls. Air dissolved in the organic liquid has no harmful effect.

When using a ball mill, it is of course desirable to use balls made of a material which does not react with the graphite and which does not wear unduly during the grinding. Vibratory ball mills usually contain steel balls and these are suitable for the present purpose.

A suitable vibratory ball mill is sold under the trade name Me-gapact. The grinding effect is produced by the impact of the balls upon the graphite and upon each other.

Separation of the balls from the graphite/ liquid mixture after grinding is easily effected by sieving.

Separation of the bulk of the organic liquid from the oleophilic graphite may be carried out by any suitable means, for example, by evaporation of the liquid. Where a high boiling or viscous liquid is used, it :may be necessary first of all to displace it by washing with a lighter liquid.

It will not usually be possible to separate the whole of the organic liquid from the graphite but the presence of small amounts of the liquid in the oleophilic graphite is not usually a disadvantage and may even be an advantage in certain applications of the product. For most purposes a liquid content of not more than 10% wt. in the oleophilic graphite is desirable after the separation process; the retained liquid will be mainly adsorbed liquid.

The superiority of oleophilic graphite for preferential separation is shown in Table 11 below. Two oleophilic graphite products were prepared from synthetic graphite as described below. Table 11 below compares the properties of these products with a ground graphite of similar surface area'prepared by grinding in air and with a highly adsorbent activated charcoal of very high surface area.

TABLE 11 Surface n-Dotriaconn-Butyl Alco- Area tane Absorbed hol Absorbed Absorbent lu /g from 0. 1% from 0.1%

Solution Solution in in n-heptane, n-heptane,

mg./m mg./m

(A) Graphite ground in Megapact vibration mill for minutes in n-heptaue 70 0.44 0.03 (B) Graphite ground in Megapaot vibration mill for minutes in n-heptane. 68 0.44 0. 03 (P) Graphite ground in Megapact vibration mill for 35 minutes in air 68 0. 38 0. 10 (Q) Highly adsorbent activated charcoal 1, 345 0. 07

it will be seen that the two oleophilic graphites (A and B) have a higher adsorption capacity for n-parafiins than a graphite (P) of similar surface area prepared by grinding in air and a much lower adsorption capacity for polar compounds. The oleophilic graphites also had a very much higher capacity for adsorbing n-paraffins than the activated charcoal (Q) which was known to have a high adsorptive capacity for n-paraflins.

The enhanced oleophilic properties of the oleophilic graphites was further demonstrated by measuring the heats of preferential adsorption of n-dotriacontane and nbutyl alcohol on graphites B and P using the Flow Microcalorimeter as described in Chemistry and Industry 20th March 1965, pp. 482-489. The results are given in Table 12.

The mill used for the grinding is a vibratory ball mill called by the manufacturer a Megapact mill. The grinding chambers are steel cylinders of 1% inch internal diameter by 15 inches long and are nearly filled with inch diameter steel balls. The mill is fitted with a one eighth horsepower electric motor and the oscillation can be adjusted from 1 to 4 mm. In operation, each cylinder was filled completely with the n-heptane and the steel balls and 25 to 30 grams of graphite were added. This left about 150 to 200 cc. n-heptane in each cylinder. The ends were then sealed with metal caps fitted with rubber washers and the grinding was carried out. After grinding, the contents of the cylinders Were placed in sieves which retained the balls and the n-heptane was removed from the oleophilic graphite by evaporation.

The oleophilic graphites described herein are also suitable for use as thickeners for high molecular Weight organic liquids, unlike graphite ground in air.

I claim:

1. A method of separating long-chain normal hydr0- carbons having at least 10 carbon atoms per molecule from their mixtures with other hydrocarbons comprising contacting the mixture with graphite having a surface area of at least about m. /gm., to adsorb selectively the normal hydrocarbons.

2. A method as claimed in claim 1 wherein the separation is carried out in the presence of a solvent which is lower-boiling than the feedstock, and is selected from benzene, n-heptane, iso-octane, ethyl alcohol, and petroleurn ether.

3. A method as claimed in claim 2 wherein the feedstock mixture is contacted with the graphite in the form of a dilute solution containing between about 0.01% and 10% (weight per volume) of the normal hydrocarbons.

4. A method as claimed in claim 1 wherein the surface area of the graphite is within the range of about 300 to 700 m. gm.

5. A method as claimed in claim 1 wherein the graphite employed is oleophilic graphite.

6. A method as claimed in claim 5 wherein the oleophilic graphite is prepared by grinding graphite in an organic liquid substantially non-reactive with graphite under the treatment conditions and having a boiling point below about 500 C. and a viscosity below about 600 centistokes at F., the amount of graphite in the organic liquid during grinding being not in excess of 50% by weight. 1

7. A method as claimed in claim 6 wherein air is substantially excluded during the grinding of the graphite.

8. A method as claimed in claim 1 wherein the separation is carried out at a temperature within the range of about 50 C. to +50 C.

9. A method of dewaxing petroleum fractions comprising treating the fraction with graphite in accordance with claim 1.

References Cited UNITED STATES PATENTS P. E. KONOPKA, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,338 ,815 August 29 1967 Aleksander Jerzy Groszek It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6 line 33 for "absorbs" read adsorbs columns 5 and 6 TABLE 7 first column, line 2 thereof, insert a closing parenthesis after "eluted"; column 7 line 3 for "carired" read carried line 8 strike out "and"; column 8 TABLE 11 heading to the first column, for "Absorbent" read Adsorbent same table in the headings to the third and fourth columns line 2 thereof, for "Absorbed", each occurrence read Adsorbed Signed and sealed this 15th day of October 1968 (SEAL) Attcst:

Edward M. Fletcher, Jr. EDWARD J. BRENNER Attcsting Officer Commissioner of Patents 

1. A METHOD OF SEPARATING LONG-CHAIN NORMAL HYDROCARBONS HAVING AT LEAST 10 CARBON ATOMS PER MOLECULE FROM THEIR MIXTURES WITH OTHER HYDROCARBONS COMPRISING CONTACTING THE MIXTURE WITH GRAPHITE HAVING A SURFACE AREA OF AT LEAST ABOUT 50 M.2/GM., TO ADSORB SELECTIVELY THE NORMAL HYDROCARBONS.
 9. A METHOD OF DEWAXING PETROLEUM FRACTIONS COMPRISING TREATING THE FRACTION WITH GRAPHITE IN ACCORDANCE WITH CLAIM
 1. 